Molecular sieve ssz-116, its synthesis and use

ABSTRACT

A novel synthetic crystalline aluminogermanosilicate molecular sieve material, designated SSZ-116, is provided. SSZ-116 can be synthesized using 3-[(3,5-di-tert-butylphenyl)methyl]-1,2-dimethyl-1H-imidazolium cations as a structure directing agent. SSZ-116 may be used in organic compound conversion reactions and/or sorptive processes.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. patent applicationSer. No. 17/023,709, filed Sep. 17, 2020, which claims priority to andthe benefit of U.S. Provisional Patent Application No. 62/962,032, filedJan. 16, 2020, the disclosures of which are incorporated herein byreference in their entirety.

FIELD

This disclosure relates to a novel synthetic crystalline molecular sievedesignated SSZ-116, its synthesis, and its use in organic compoundconversion reactions and sorption processes.

BACKGROUND

Molecular sieves are a commercially important class of materials thathave distinct crystal structures with defined pore structures that areshown by distinct X-ray diffraction (XRD) patterns and have specificchemical compositions. The crystal structure defines cavities and poresthat are characteristic of the specific type of molecular sieve.

According to the present disclosure, a new crystalline molecular sieve,designated SSZ-116 and having a unique powder X-ray diffraction pattern,has been synthesized using3-[(3,5-di-tert-butylphenyl)methyl]-1,2-dimethyl-1H-imidazolium cationsas a structure directing agent.

SUMMARY

In a first aspect, there is provided a molecular sieve having, in itsas-synthesized form, a powder X-ray diffraction pattern including atleast the peaks in Table 3 below.

In its as-synthesized and anhydrous form, the molecular sieve can have achemical composition comprising the following molar relationship:

Broadest Secondary TO₂/Al₂O₃ ≥30 ≥50 Q/TO₂ >0 to 0.1 >0 to 0.1wherein T is a tetravalent element comprising silicon and germanium; andQ comprises3-[(3,5-di-tert-butylphenyl)methyl]-1,2-dimethyl-1H-imidazolium cations.

In a second aspect, there is provided a molecular sieve having, in itscalcined form, a powder X-ray diffraction pattern including at least thepeaks in Table 4 below.

In its calcined form, the molecular sieve can have a chemicalcomposition comprising the following molar relationship:

Al₂O₃:(n)TO₂

wherein n is ≥30; and T is a tetravalent element comprising silicon andgermanium.

In a third aspect, there is provided a method of synthesizing themolecular sieve described herein, the method comprising (a) providing areaction mixture comprising: (1) a FAU framework type zeolite; (2) asource of germanium; (3) a structure directing agent comprising3-[(3,5-di-tert-butylphenyl)methyl]-1,2-dimethyl-1H-imidazolium cations(Q); (4) a source of fluoride ions; and (5) water; and (b) subjectingthe reaction mixture to crystallization conditions sufficient to formcrystals of the molecular sieve.

In a fourth aspect, there is provided a process of converting afeedstock comprising an organic compound to a conversion product whichcomprises contacting the feedstock at organic compound conversionconditions with a catalyst comprising the molecular sieve describedherein.

In a fifth aspect, there is provided an organic nitrogen compoundcomprising a cation having the following structure:

DETAILED DESCRIPTION Definitions

The term “framework type” has the meaning described in the “Atlas ofZeolite Framework Types,” by Ch. Baerlocher and L.B. McCusker and D.H.Olsen (Elsevier, Sixth Revised Edition, 2007).

The term “zeolite” refers a synthetic aluminosilicate molecular sievehaving a framework constructed of alumina and silica (i.e., repeatingSiO₄ and AlO₄ tetrahedral units).

The term “aluminogermanosilicate” refers to a crystalline microporoussolid including aluminum, germanium and silicon oxides within itsframework structure. The aluminogermanosilicate may be a“pure-aluminogermanosilicate” (i.e., absent other detectable metaloxides with its framework structure) or optionally substituted. Whendescribed as “optionally substituted,” the respective framework maycontain other atoms (e.g., B, Ga, In, Fe, Ti, Zr) substituted for one ormore of the atoms not already present in the parent framework.

The term “as-synthesized” is employed herein to refer to a molecularsieve in its form after crystallization, prior to removal of thestructure directing agent.

The term “anhydrous” is employed herein to refer to a molecular sievesubstantially devoid of both physically adsorbed and chemically adsorbedwater.

As used herein, the numbering scheme for the Periodic Table Groups is asdisclosed in Chem. Eng. News 1985, 63(5), 26-27.

Synthesis of the Molecular Sieve

Molecular sieve SSZ-116 may be synthesized by: (a) providing a reactionmixture comprising (1) a FAU framework type zeolite; (2) a source ofgermanium; (3) a structure directing agent comprising3-[(3,5-di-tert-butylphenyl)methyl]-1,2-dimethyl-1H-imidazolium cations(Q); (4) a source of fluoride ions; and (5) water; and (b) subjectingthe reaction mixture to crystallization conditions sufficient to formcrystals of the molecular sieve.

The reaction mixture can have a composition, in terms of molar ratios,within the ranges set forth in Table 1:

TABLE 1 Reactants Broadest Secondary TO₂/Al₂O₃  30 to 600  60 to 500Q/TO₂ 0.10 to 1.00 0.20 to 0.70 F/TO₂ 0.10 to 1.00 0.20 to 0.70 H₂O/TO₂ 2 to 10 4 to 8wherein T is a tetravalent element comprising silicon and germanium; andQ comprises3-[(3,5-di-tert-butylphenyl)methyl]-1,2-dimethyl-1H-imidazolium cations.

The FAU framework type zeolite can be the only silica and aluminumsource. The FAU framework type zeolite can be zeolite Y. The FAUframework type zeolite can comprise two or more zeolites. The two ormore zeolites can be Y zeolites having different silica-to-alumina molarratios.

Suitable sources of germanium include germanium dioxide and germaniumalkoxides (e.g., tetraethoxygermanium, tetraisopropoxygermanium).

The reaction mixture may have a molar ratio of SiO₂/GeO₂ in a range offrom 4 to 12 (e.g., 6 to 10).

Suitable sources of fluoride ions include hydrogen fluoride, ammoniumfluoride, and ammonium bifluoride.

SSZ-116 is synthesized using a structure directing agent comprising3-[(3,5-di-tert-butylphenyl)methyl]-1,2-dimethyl-1H-imidazolium cations(Q), represented by the following structure (1):

Suitable sources of Q are the hydroxides and/or other salts of thequaternary ammonium compound.

The reaction mixture may have a molar ratio of Q/F in a range of from0.80 to 1.20 (e.g., 0.85 to 1.15, 0.90 to 1.10, 0.95 to 1.05, or 1 to1).

The reaction mixture may contain seeds of a molecular sieve material,such as SSZ-116 from a previous synthesis, in an amount of from 0.01 to10,000 ppm by weight (e.g., 100 to 5000 ppm by weight) of the reactionmixture. Seeding can be advantageous in decreasing the amount of timenecessary for complete crystallization to occur. In addition, seedingcan lead to an increased purity of the product obtained by promoting thenucleation and/or formation of SSZ-116 over any undesired phases.

It is noted that the reaction mixture components can be supplied by morethan one source. Also, two or more reaction components can be providedby one source. The reaction mixture can be prepared either batchwise orcontinuously.

Crystallization and Post-Synthesis Treatment

Crystallization of the molecular sieve from the above reaction mixturecan be carried out under either static, tumbled or stirred conditions ina suitable reactor vessel (e.g., a polypropylene jar or a Teflon-linedor stainless-steel autoclave) placed in a convection oven at atemperature of from 125° C. to 200° C. for a time sufficient forcrystallization to occur at the temperature used (e.g., 1 day to 14days). The hydrothermal crystallization process is typically conductedunder pressure, such as in an autoclave, and is preferably underautogenous pressure.

Once the molecular sieve crystals have formed, the solid product isseparated from the reaction mixture by standard separation techniquessuch as centrifugation or filtration. The recovered crystals arewater-washed and then dried, for several seconds to a few minutes (e.g.,5 seconds to 10 minutes for flash drying) or several hours (e.g., about4 to 24 hours for oven drying at 75° C. to 150° C.), to obtainas-synthesized molecular sieve crystals. The drying step can beperformed at atmospheric pressure or under vacuum.

As a result of the crystallization process, the recovered crystallinemolecular sieve product contains within its pore structure at least aportion of the structure directing agent used in the synthesis.

The as-synthesized molecular sieve may be subjected to treatment toremove part or all of the structure directing agent used in itssynthesis. This is conveniently effected by thermal treatment (e.g.,calcination) in which the as-synthesized molecular sieve is heated at atemperature sufficient to remove part or all of the structure directingagent. The thermal treatment may be carried out in any mannerconventionally known in the art. Suitable conditions include heating ata temperature of at least 300° C. (e.g., at least about 370° C.) for atleast 1 minute and generally not longer than 20 hours, for example, fora period of from 1 hour to 12 hours. While sub-atmospheric pressure canbe employed for the thermal treatment, atmospheric pressure is desiredfor reasons of convenience. The thermal treatment can be performed at atemperature up to about 925° C. For instance, the thermal treatment canbe conducted at a temperature of from 400° C. to 600° C. in the presenceof an oxygen-containing gas.

Any extra-framework cations in the molecular sieve can be replaced inaccordance with techniques well known in the art (e.g., by ion exchange)with hydrogen, ammonium, or any desired metal cation.

Characterization of the Molecular Sieve

In its as-synthesized and anhydrous form, molecular sieve SSZ-116 canhave a chemical composition comprising the following molar relationshipset forth in Table 2:

TABLE 2 Broadest Secondary TO₂/Al₂O₃ ≥30 ≥50 Q/TO₂ >0 to 0.1 >0 to 0.1wherein T is a tetravalent element comprising silicon and germanium; andQ comprises3-[(3,5-di-tert-butylphenyl)methyl]-1,2-dimethyl-1H-imidazolium cations.In some aspects, the molecular sieve can have a SiO₂/GeO₂ molar ratio ina range of 4 to 12 (e.g., 6 to 10).

In its calcined form, molecular sieve SSZ-116 can have a chemicalcomposition comprising the following molar relationship:

Al₂O₃:(n)TO₂

wherein n is ≥30 (e.g., 30 to 500, ≥50, 50 to 250, or 50 to 150); and Tis a tetravalent element comprising silicon and germanium.

Molecular sieve SSZ-116 is characterized by a powder XRD pattern, which,in the as-synthesized form of the molecular sieve, includes at least thepeaks set forth in Table 3, and which, in the calcined form of themolecular sieve, includes at least the peaks set forth in Table 4.

TABLE 3 Characteristic Peaks for As-Synthesized SSZ-116 2-Theta^((a))[°] d-Spacing [Å] Relative Intensity 8.59 10.29 m 11.11 7.96 w 15.655.66 vs 17.49 5.07 w 20.87 4.25 m 23.02 3.86 m 23.60 3.77 w 24.05 3.70 w25.30 3.52 m 25.90 3.44 m 26.91 3.31 w ^((a))±0.30

TABLE 4 Characteristic Peaks for Calcined SSZ-116 2-Theta^((a)) [°]d-Spacing [Å] Relative Intensity 8.68 10.18 vs 11.23 7.87 w 15.60 5.68vs 17.68 5.01 vs 20.79 4.27 m 23.14 3.84 w 23.56 3.77 w 23.98 3.71 w25.20 3.53 w 25.83 3.42 vs 26.83 3.32 w ^((a))±0.30

The powder X-ray diffraction patterns presented herein were collected bystandard techniques. The radiation was CuKα radiation. The interplanarspacings, d-spacings, were calculated in Angstrom units, and therelative intensities of the lines, I/I₀, represents the ratio of thepeak intensity to the intensity of the strongest line, above background.The intensities are uncorrected for Lorentz and polarization effects.The relative intensities are given in terms of the following notations:w (weak) is <20; m (medium) is ≥20 to <40; s (strong) is ≥40 to <60; andvs (very strong) is ≥60.

Minor variations in the diffraction pattern can result from variationsin the mole ratios of the framework species of the sample due to changesin lattice constants. In addition, disordered materials and/orsufficiently small crystals will affect the shape and intensity ofpeaks, leading to significant peak broadening. Minor variations in thediffraction pattern can also result from variations in the organiccompound used in the preparation. Calcination can also cause minorshifts in the XRD pattern. Notwithstanding these minor perturbations,the basic crystal lattice structure remains unchanged.

Sorption and Catalysis

Molecular sieve SSZ-116 (where part or all of the structure directingagent is removed) may be used as a sorbent or as a catalyst to catalyzea wide variety of organic compound conversion processes including manyof present commercial/industrial importance. Examples of chemicalconversion processes which are effectively catalyzed by SSZ-116, byitself or in combination with one or more other catalytically activesubstances including other crystalline catalysts, include thoserequiring a catalyst with acid activity. Examples of organic conversionprocesses which may be catalyzed by SSZ-116 include cracking,hydrocracking, disproportionation, alkylation, oligomerization,aromatization, and isomerization.

As in the case of many catalysts, it may be desirable to incorporateSSZ-116 with another material resistant to the temperatures and otherconditions employed in organic conversion processes. Such materialsinclude active and inactive materials and synthetic or naturallyoccurring zeolites as well as inorganic materials such as clays, silicaand/or metal oxides such as alumina. The latter may be either naturallyoccurring, or in the form of gelatinous precipitates or gels, includingmixtures of silica and metal oxides. Use of a material in conjunctionwith SSZ-116 (i.e., combined therewith or present during synthesis ofthe new material) which is active, tends to change the conversion and/orselectivity of the catalyst in certain organic conversion processes.Inactive materials suitably serve as diluents to control the amount ofconversion in a given process so that products can be obtained in aneconomic and orderly manner without employing other means forcontrolling the rate of reaction. These materials may be incorporatedinto naturally occurring clays (e.g., bentonite and kaolin) to improvethe crush strength of the catalyst under commercial operatingconditions. These materials (i.e., clays, oxides, etc.) function asbinders for the catalyst. It is desirable to provide a catalyst havinggood crush strength because in commercial use it is desirable to preventthe catalyst from breaking down into powder-like materials. These clayand/or oxide binders have been employed normally only for the purpose ofimproving the crush strength of the catalyst.

Naturally occurring clays which can be composited with SSZ-116 includethe montmorillonite and kaolin family, which families include thesub-bentonites, and the kaolins commonly known as Dixie, McNamee,Georgia and Florida clays or others in which the main mineralconstituent is halloysite, kaolinite, dickite, nacrite, or anauxite.Such clays can be used in the raw state as originally mined or initiallysubjected to calcination, acid treatment or chemical modification.Binders useful for compositing with SSZ-116 also include inorganicoxides, such as silica, zirconia, titania, magnesia, beryllia, alumina,and mixtures thereof.

In addition to the foregoing materials, SSZ-116 can be composited with aporous matrix material such as silica-alumina, silica-magnesia,silica-zirconia, silica-thoria, silica-beryllia, silica-titania as wellas ternary compositions such as silica-alumina-thoria,silica-alumina-zirconia silica-alumina-magnesia andsilica-magnesia-zirconia.

The relative proportions of SSZ-116 and inorganic oxide matrix may varywidely, with the SSZ-116 content ranging from 1 to 90 wt. % (e.g., 2 to80 wt. %) of the composite.

EXAMPLES

The following illustrative examples are intended to be non-limiting.

EXAMPLE 1 Synthesis of3-[(3,5-di-tert-butylphenyl)methyl]-1,2-dimethyl-1H-imidazoliumhydroxide

A 100 mL round bottom flask equipped with a magnetic stir bar wascharged with 8 g of 3,5-di-tert-butylbenzyl bromide, 2.99 g of1,2-dimethylimidazole and 60 mL of toluene. A reflux condenser was thenattached, and the mixture heated at 96° C. for 24 hours. After cooling,the mixture was filtered, and the solid residue was washed with ethylacetate. The solids were then dried under vacuum.

The resulting bromide salt was exchanged to the corresponding hydroxidesalt by stirring it with hydroxide exchange resin in deionized waterovernight. The solution was filtered, and the filtrate was analyzed forhydroxide concentration by titration of a small sample with a standardsolution of 0.1 N HCl.

EXAMPLE 2 Synthesis of SSZ-116

Into a tared 23 mL Parr reactor was added 0.27 g of Tosoh 390HUAY-zeolite (SiO₂/Al₂O₃ molar ratio˜300), 0.05 g of GeO₂ and 2.5 mmoles ofan aqueous3-[(3,5-di-tert-butylphenyl)methyl]-1,2-dimethyl-1H-imidazoliumhydroxide solution. The reactor was then placed in a vented hood andwater was allowed to evaporate to bring the H₂O/SiO₂+GeO₂) molar ratioto 7 (as determined by the total mass of the suspension). Then, HF (2.5mmoles) was added and the reactor was heated to 160° C. with tumbling at43 rpm for about 7 days. The solid products were recovered bycentrifugation, washed with deionized water and dried at 95° C.

Powder XRD showed the product to be a pure form of a new phase, SSZ-116.

The product had a SiO₂/GeO₂ molar ratio of 8.

EXAMPLE 3 Calcination of SSZ-116

The as-synthesized molecular sieve of Example 1 was calcined inside amuffle furnace under a flow of air at 550° C. for 5 hours, then cooledand analyzed by powder XRD.

The powder XRD pattern of the calcined material indicated that thematerial remains stable after calcination to remove the structuredirecting agent.

EXAMPLE 4 Micropore Volume Analysis

Analysis of the calcined form of SSZ-116 by the t-plot method ofnitrogen physisorption shows the sample possesses 38.00 m²/g externalsurface area and 0.1178 cm³/g micropore volume. All N₂ adsorptionisotherms were performed at 77 K with a TriStar II instrument(Micromeritics). Prior to analysis, the samples were outgassed undervacuum at 400° C. The t-plot method was used to calculate the microporevolumes on the adsorption branch.

Analysis of the hydrogen form of SSZ-116 by the t-plot method of argonphysisorption shows the sample possesses 51.552 m²/g external surfacearea and 0.058 cm³/g micropore volume. Argon physisorption was conductedon a Quantachrome Autosorb iQ instrument. Prior to adsorptionmeasurements, samples were outgassed by heating (at a rate of 10°C./min) the sample under vacuum for 1 hour at 80° C., 3 hours at 120° C.and 10 hours at 350° C. Adsorption isotherms were collected using argonat 87.45 K using the constant dose (quasi-equilibrium) method. Microporevolumes were obtained from the adsorption branch of the isotherms usingthe t-plot method (0.1<P/P₀<0.3).

EXAMPLE 5 Constraint Index Testing

Constraint Index (CI) is a test describing the relative propensity of amaterial to crack linear alkanes versus branched alkanes. Thecompetitive cracking of n-hexane versus 3-methylpentane was firstdescribed by W.O. Haag et al. (J. Catal. 1981, 67, 218-222). Additionalwork to help clarify results of the test have been performed by S.I.Zones et al. (Micropor. Mesopor. Mater. 2000, 35-36, 31-46) and M.E.Davis et al. (J. Catal. 2010, 269, 64-70). The CI value may becalculated using Equation 1 (X denotes the fractional conversion of eachspecies) and thus it is proportional to the observed cracking rateconstants of n-hexane (nC₆) to 3-methylpentane (3MP).

$\begin{matrix}{{CI} = \frac{\log\left( {1 - X_{{nC}6}} \right)}{\log\left( {1 - X_{3MP}} \right)}} & \left( {{Equation}1} \right)\end{matrix}$

As is typically reported, small pore zeolites usually exhibit CI valuesgreater than 12; medium pore zeolites often exhibit CI values in a rangeof from 2 to 12; and large pore zeolites usually exhibit CI values ofless than 1.

The hydrogen form of SSZ-116 prepared per Example 4 was pelletized at 4kpsi, crushed and granulated to 20-40 mesh. A 0.6 g sample of thegranulated material was calcined in air at 540° C. for 4 hours andcooled in a desiccator to ensure dryness. Then, 0.47 g of material waspacked into a ¼ inch stainless steel tube with alundum on both sides ofthe molecular sieve bed. A furnace (Applied Test Systems, Inc.) was usedto heat the reactor tube. Nitrogen was introduced into the reactor tubeat 9.4 mL/min and at atmospheric pressure. The reactor was heated toabout 800° F. (427° C.), and a 50/50 feed of n-hexane and3-methylpentane (3MP) was introduced into the reactor at a rate of 8μ/min. The feed was delivered by an ISCO pump. Direct sampling into a GCbegan after 15 minutes of feed introduction. Test data results after 15minutes on stream (800° F.) are presented in Table 5.

TABLE 5 Constraint Index Test n-Hexane Conversion, % 0.2 3-MethylpentaneConversion, % 0.6 Feed Conversion, % 0.4 Constraint Index (excluding2MP) 0.35 Constraint Index (including 2MP) 0.36

EXAMPLE 6

Example 2 was repeated except that CBV-780 Y-zeolite (SiO₂/Al₂O₃ molarratio=80; Zeolyst International) was used as the FAU source. Powder XRDshowed the product to be SSZ-116.

EXAMPLE 7

Example 2 was repeated except that CBV-760 Y-zeolite (SiO₂/Al₂O₃ molarratio=60; Zeolyst International) was used as the FAU source. Powder XRDshowed the product to be SSZ-116.

Elemental analysis showed that the product had a silicon content of 14.7wt. %, a germanium content of 4.8 wt. %, an aluminum content of 0.34 wt.%, a Si/Ge molar ratio of 7.66, and a (SiO₂+GeO₂)/Al₂O₃ molar ratio of95.

EXAMPLE 8

Example 2 was repeated except that CBV-720 Y-zeolite (SiO₂/Al₂O₃ molarratio=30; Zeolyst International) was used as the FAU source. Powder XRDshowed the product to be SSZ-116. As-synthesized SSZ-116 was calcined asdescribed in Example 3.

Analysis of calcined SSZ-116 by the t-plot method of nitrogenphysisorption shows the sample possessed a micropore volume of 0.11cm³/g.

EXAMPLE 9 Brønsted Acidity

Brønsted acidity of the molecular sieve of Example 8 in its calcinedform was determined by n-propylamine temperature-programmed desorption(TPD) adapted from the published descriptions by T.J. Gricus Kofke etal. (J. Catal. 1988, 114, 34-45); T.J. Gricus Kofke et al. (J. Catal.1989, 115, 265-272); and J.G. Tittensor et al. (J. Catal. 1992, 138,714-720). A sample was pre-treated at 400° C-500° C. for 1 hour inflowing dry H₂. The dehydrated sample was then cooled down to 120° C. inflowing dry helium and held at 120° C. for 30 minutes in a flowinghelium saturated with n-propylamine for adsorption. Then-propylamine-saturated sample was then heated up to 500° C. at a rateof 10° C./minute in flowing dry helium. The Brønsted acidity wascalculated based on the weight loss vs. temperature by thermogravimetricanalysis (TGA) and effluent NH₃ and propene by mass spectrometry. Thesample had a Brønsted acidity of 90.07 mmol/g, indicating that aluminumsites are incorporated into the framework of the molecular sieve.

1. A molecular sieve having, in its calcined form, a powder X-raydiffraction pattern including the following peaks: 2-Theta [±0.30°]d-Spacing [Å] Relative Intensity 8.68 10.18 vs 11.23 7.87 w 15.60 5.68vs 17.68 5.01 vs 20.79 4.27 m 23.14 3.84 w 23.56 3.77 w 23.98 3.71 w25.20 3.53 w 25.83 3.42 vs 26.83 3.32  w.


2. The molecular sieve of claim 1, and having a composition comprisingthe molar relationship:Al₂O₃:(n)TO₂ wherein n is ≥30; and T is a tetravalent element comprisingsilicon and germanium.
 3. The molecular sieve of claim 1, and having acomposition comprising the molar relationship:Al₂O₃:(n)TO₂ wherein n is ≥50; and T is a tetravalent element comprisingsilicon and germanium.
 4. A molecular sieve having, in itsas-synthesized form, a powder X-ray diffraction pattern including thefollowing peaks: 2-Theta [±0.30°] d-Spacing [Å] Relative Intensity 8.5910.29 m 11.11 7.96 w 15.65 5.66 vs 17.49 5.07 w 20.87 4.25 m 23.02 3.86m 23.60 3.77 w 24.05 3.70 w 25.30 3.52 m 25.90 3.44 m 26.91 3.31  w.


5. The molecular sieve of claim 4, having a chemical compositioncomprising the following molar relationship: TO₂/Al₂O₃ ≥30 Q/TO₂ >0 to0.1

wherein T is a tetravalent element comprising silicon and germanium; andQ comprises3-[(3,5-di-tert-butylphenyl)methyl]-1,2-dimethyl-1H-imidazolium cations.6. The molecular sieve of claim 4, having a chemical compositioncomprising the following molar relationship: TO₂/Al₂O₃ ≥50 Q/TO₂ >0 to0.1

wherein T is a tetravalent element comprising silicon and germanium; andQ comprises3-[(3,5-di-tert-butylphenyl)methyl]-1,2-dimethyl-1H-imidazolium cations.